US5597576A - Oil-based transparent gels - Google Patents
Oil-based transparent gels Download PDFInfo
- Publication number
- US5597576A US5597576A US08/274,447 US27444794A US5597576A US 5597576 A US5597576 A US 5597576A US 27444794 A US27444794 A US 27444794A US 5597576 A US5597576 A US 5597576A
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- United States
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- viscosity
- oil
- fatty alcohols
- formulation
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- Expired - Fee Related
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- 239000000499 gel Substances 0.000 title abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000009472 formulation Methods 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 22
- -1 malic acid diesters Chemical class 0.000 claims abstract description 17
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011975 tartaric acid Substances 0.000 claims abstract description 14
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 239000002537 cosmetic Substances 0.000 claims abstract description 9
- 239000001630 malic acid Substances 0.000 claims abstract description 9
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011090 malic acid Nutrition 0.000 claims abstract description 8
- 235000019198 oils Nutrition 0.000 claims description 20
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 17
- 229910021485 fumed silica Inorganic materials 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 11
- 229960004063 propylene glycol Drugs 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 229940119170 jojoba wax Drugs 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 229960001679 octinoxate Drugs 0.000 claims description 5
- 150000005691 triesters Chemical class 0.000 claims description 5
- 229940093476 ethylene glycol Drugs 0.000 claims description 4
- 239000008168 almond oil Substances 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019489 Almond oil Nutrition 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 10
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 9
- 239000006071 cream Substances 0.000 description 7
- 239000003349 gelling agent Substances 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- 241000612703 Augusta Species 0.000 description 4
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000546 pharmaceutical excipient Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 244000144725 Amygdalus communis Species 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000001857 anti-mycotic effect Effects 0.000 description 2
- 239000002543 antimycotic Substances 0.000 description 2
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002632 lipids Chemical group 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 101100389259 Echinococcus multilocularis EM13 gene Proteins 0.000 description 1
- 241000221095 Simmondsia Species 0.000 description 1
- 235000004433 Simmondsia californica Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003246 corticosteroid Substances 0.000 description 1
- 229960001334 corticosteroids Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- YBGZDTIWKVFICR-UHFFFAOYSA-N octinoxate Chemical compound CCCCC(CC)COC(=O)C=CC1=CC=C(OC)C=C1 YBGZDTIWKVFICR-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0014—Skin, i.e. galenical aspects of topical compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/005—Preparations for sensitive skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/06—Preparations for care of the skin for countering cellulitis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
- A61K2800/31—Anhydrous
Definitions
- This invention relates to oil-based transparent gels characterised by a wide viscosity range, for use in the pharmaceutical and cosmetics sectors.
- the gels contain tartaric acid or malic acid diesters of C 12 -C 13 single-branch fatty alcohols, possibly mixed with oils and other compounds such as silica and polyalcohols.
- Lipogels are physico-chemical structures which, if obtained in clear form, enable formulations to be prepared having a consistency similar to or even better than creams or modern gel emulsions, without the use of cellulose methacrylic polymers or other compounds typical of aqueous systems.
- Transparent lipogels have a particularly pleasing appearance, and compared with aqueous formulations have the advantage of not requiring preservatives and of being able to be used in very small quantity.
- lipogels Another important advantage of lipogels is the ability to obtain lipid structures with differing performance in terms of skin feeling, greasiness and the possibility of inserting liposoluble and water-soluble active principles, these being characteristics which facilitate the development of final applications.
- the literature describes various processes for preparing transparent lipogels.
- Japanese patent 63223083 describes the preparation of transparent lipogels by heating mixtures formed from terpenes, paraffins and/or polyalcohols (oil base) and ionic surfactants deriving from fatty acids to 80° C., followed by slow cooling.
- the need to heat the mixtures results however in a considerable increase in the preparation costs of such formulations.
- Japanese patent 4059716 describes transparent lipogels prepared by cold-mixing pyrogenic silica with a non-ionic surfactant and a oily component consisting of a malic ester and olive oil.
- the formulations obtained have however only a moderate viscosity (7.5 Pa.s) which limits their use for specific applications.
- An alternative method consists of using the vegetable origin gelling agent for oily components known by the commercial name of GP-100®, marketed by Ajinomoto, which enables transparent gels to be obtained without the presence of adjuvants.
- the preparation method again comprises heating the mixture to about 80°-85° C.
- the gelling agent cost is high and the consistency of the gels obtained is rather low.
- the present invention therefore provides transparent lipogels for cosmetics and pharmaceutical use having the following composition:
- tartaric acid diester of C 12 -C 13 single-branch fatty alcohols in a quantity of between 46 and 95 wt %
- sweet almond oil in a quantity of between 1 and 46%
- PEG polyethyleneglycol 200
- glycerin in a quantity of between 1 and 10%.
- the viscosity of the gels of our invention varies considerably in relation to the composition of the different systems and can be regulated on the basis of the type of silica and type of co-gelling agent (polyalcohol), hence enabling the field of final applications to be widened.
- the tartaric or malic acid diesters of C 12 -C 13 single-branch fatty alcohols are completely compatible with the most widely used cosmetics excipients in the preparation of formulations, even in high proportion (1:1, w/w), these including for example white oils, vegetable oils (jojoba, sweet almond), solid and liquid solar filters (EU-SOLEX and PARSOL CMX respectively) and Cosmacol esters (EOI and ECI).
- Body products such as anticellulitis, etc.
- gels and detergents for the hair, hands and body can be prepared, as well as bath oils.
- topical medicaments can be formulated as lipogels, which have the advantage of making their application more pleasant than traditional ointment formulations.
- Topical medicaments can consequently be prepared with corticosteroids or antimycotics, or galenic preparations be produced containing sulphur, zinc oxide, resorcinol, ichthyol etc.
- galenic preparations be produced containing sulphur, zinc oxide, resorcinol, ichthyol etc.
- antimycotic, antiseptic and detergent preparations they contribute considerably to the active principle, with no interference with preservatives.
- the lipogels of the present invention could also be of interest for other products, such as shoe creams, wood polishing products, hand washing pastes and in other sectors where solid or semi-solid lipid structures are required.
- the tartaric acid diester of C 12 -C 13 single-branch fatty alcohols is known by the name COSMACOL ETI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
- the malic acid diester of C 12 -C 13 single-branch fatty alcohols is known by the name COSMACOL EMI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
- the 2-ethyl-hexanoic acid alkyl (C 12 -C 13 single-branch) ester is known by the name COSMACOL EOI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
- benzophenone-6 is known by the name EUSOLEX® 4360 and is marketed by MERCK;
- ethylhexyl-p-methoxy-cinnamate is known by the name PARSOL MCX® and is marketed by GIVAUDAN.
- the transparent gels are prepared under cold conditions by mild mechanical agitation. Heating to 35°-40° C. is necessary only if glycerin is used.
- the last stage of the preparation consists of adding the co-gelling agent (polyalcohols) in the desired quantity, followed by agitation of the mixture.
- the pyrogenic silica can be used either as such (hence hydrophilic) or silanized (hence hydrophobic).
- the minimum pyrogenic silica concentration which enables transparent gels to be obtained is less than 3 wt % for the hydrophilic type, whereas for the silanized type (hydrophobic) it is greater than 3.5 wt % but less than 5 wt %.
- composition ET19 according to the invention 100 g of the composition ET19 according to the invention were prepared, it consisting of:
- composition was prepared by mixing components a and b together under cold conditions using a mechanical stirrer or turboagitator. While agitating the obtained homogeneous solution with a turbomixer at moderate speed, component c and finally component d were added.
- the viscosity (expressed in Pascal/second) was determined as described on page 6.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Birds (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Emergency Medicine (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
Abstract
Oil-based gels are described containing tartaric or malic acid diesters possibly mixed with oils, and other components such as silica and polyalcohols. The gels are characterized by a wide viscosity range and can find application in the preparation of formulations for cosmetics and pharmaceutical use.
Description
This invention relates to oil-based transparent gels characterised by a wide viscosity range, for use in the pharmaceutical and cosmetics sectors.
The gels contain tartaric acid or malic acid diesters of C12 -C13 single-branch fatty alcohols, possibly mixed with oils and other compounds such as silica and polyalcohols.
Lipogels are physico-chemical structures which, if obtained in clear form, enable formulations to be prepared having a consistency similar to or even better than creams or modern gel emulsions, without the use of cellulose methacrylic polymers or other compounds typical of aqueous systems.
Transparent lipogels have a particularly pleasing appearance, and compared with aqueous formulations have the advantage of not requiring preservatives and of being able to be used in very small quantity.
Another important advantage of lipogels is the ability to obtain lipid structures with differing performance in terms of skin feeling, greasiness and the possibility of inserting liposoluble and water-soluble active principles, these being characteristics which facilitate the development of final applications.
However the preparation of gels with the required properties is not always easy.
The literature describes various processes for preparing transparent lipogels.
For example, Japanese patent 63223083 describes the preparation of transparent lipogels by heating mixtures formed from terpenes, paraffins and/or polyalcohols (oil base) and ionic surfactants deriving from fatty acids to 80° C., followed by slow cooling. The need to heat the mixtures results however in a considerable increase in the preparation costs of such formulations.
Japanese patent 4059716 describes transparent lipogels prepared by cold-mixing pyrogenic silica with a non-ionic surfactant and a oily component consisting of a malic ester and olive oil. The formulations obtained have however only a moderate viscosity (7.5 Pa.s) which limits their use for specific applications. An alternative method consists of using the vegetable origin gelling agent for oily components known by the commercial name of GP-100®, marketed by Ajinomoto, which enables transparent gels to be obtained without the presence of adjuvants. However the preparation method again comprises heating the mixture to about 80°-85° C. In addition the gelling agent cost is high and the consistency of the gels obtained is rather low.
We have now found that it is possible to obtain transparent lipogels characterised by a wide viscosity range by mixing tartaric or malic acid esters, possibly containing oils or any cosmetics excipient, with other compounds such as silica and polyalcohols under cold conditions, in determined proportions.
The present invention therefore provides transparent lipogels for cosmetics and pharmaceutical use having the following composition:
A) an ester chosen from:
tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 46 and 95 wt %,
malic acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 87 and 93 wt %;
B) an oil or ester chosen from:
2-ethyl-hexanoic acid alkyl (C12 -C13 single-branch) ester,
2-hydroxy-1,2,3-propanetricarboxylic acid alkyl (C12 -C13 single-branch) triester,
white oil,
jojoba oil,
benzophenone-6,
ethylhexyl-p-methoxy-cinnamate,
sweet almond oil, in a quantity of between 1 and 46%;
C) hydrophilic or hydrophobic pyrogenic silica in a quantity of between 2.8 and 7.0%;
D) a polyalcohol chosen from:
polyethyleneglycol 200 (PEG),
ethyleneglycol,
1,2-propyleneglycol,
glycerin, in a quantity of between 1 and 10%.
The viscosity of the gels of our invention varies considerably in relation to the composition of the different systems and can be regulated on the basis of the type of silica and type of co-gelling agent (polyalcohol), hence enabling the field of final applications to be widened.
The tartaric or malic acid diesters of C12 -C13 single-branch fatty alcohols are completely compatible with the most widely used cosmetics excipients in the preparation of formulations, even in high proportion (1:1, w/w), these including for example white oils, vegetable oils (jojoba, sweet almond), solid and liquid solar filters (EU-SOLEX and PARSOL CMX respectively) and Cosmacol esters (EOI and ECI).
It should also be noted that the dermotoxicological safety of the key products (Cosmacol esters, silica and glycols) makes these gels a useful addition for the formulator in ensuring certain success of both cosmetics and pharmaceutical preparations. Their possible uses in the cosmetics sector include the preparation of protective products, such as:
Sun creams with a predetermined sun protection factor
Water-repellent creams for professional use
Hand barrier creams
Face and lip creams, particularly protective for sensitive skin
Manual massage creams
Body products such as anticellulitis, etc.
In addition gels and detergents for the hair, hands and body can be prepared, as well as bath oils.
In the pharmaceutical sector, because of their special properties these lipogels can replace traditional ointments with considerable advantages, including bioavailability.
For example all topical medicaments can be formulated as lipogels, which have the advantage of making their application more pleasant than traditional ointment formulations.
Topical medicaments can consequently be prepared with corticosteroids or antimycotics, or galenic preparations be produced containing sulphur, zinc oxide, resorcinol, ichthyol etc. In specific or general antimycotic, antiseptic and detergent preparations they contribute considerably to the active principle, with no interference with preservatives.
The lipogels of the present invention could also be of interest for other products, such as shoe creams, wood polishing products, hand washing pastes and in other sectors where solid or semi-solid lipid structures are required.
All the components used in preparing the formulations are available commercially, and specifically:
the tartaric acid diester of C12 -C13 single-branch fatty alcohols is known by the name COSMACOL ETI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
The malic acid diester of C12 -C13 single-branch fatty alcohols is known by the name COSMACOL EMI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
the 2-ethyl-hexanoic acid alkyl (C12 -C13 single-branch) ester is known by the name COSMACOL EOI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
the 2-hydroxy-1,2,3-propanetricarboxylic acid alkyl (C12 -C13 single-branch) triester is known by the name COSMACOL ECI® and is marketed by ENICHEM AUGUSTA INDUSTRIALE, Milan;
benzophenone-6 is known by the name EUSOLEX® 4360 and is marketed by MERCK;
ethylhexyl-p-methoxy-cinnamate is known by the name PARSOL MCX® and is marketed by GIVAUDAN.
The transparent gels are prepared under cold conditions by mild mechanical agitation. Heating to 35°-40° C. is necessary only if glycerin is used.
It is also possible to prepare a base (consisting of Cosmacol ester and pyrogenic silica in the desired concentration) having the characteristics of a transparent viscous fluid, to which the various cosmetics excipients are added until a final formulation suitable for the required type of application is obtained.
In this case, the last stage of the preparation consists of adding the co-gelling agent (polyalcohols) in the desired quantity, followed by agitation of the mixture.
The obtaining of transparent gels is strictly dependent on the type of lipo-gelling agent used and on the chosen oil base. In addition there seems to be a particular compatibility between the esters of our invention and the various types of polyalcohol. In this respect, low polyalcohol concentrations are generally sufficient to obtain a transparent system. The required concentration is 1-2% on average.
The pyrogenic silica can be used either as such (hence hydrophilic) or silanized (hence hydrophobic). The minimum pyrogenic silica concentration which enables transparent gels to be obtained is less than 3 wt % for the hydrophilic type, whereas for the silanized type (hydrophobic) it is greater than 3.5 wt % but less than 5 wt %.
The viscosity of the formulations was determined by a BROOKFIELD rotary viscometer fitted with an RV=7 spindle at a spindle speed of 50 rpm or 20 rpm, the appearance of the formulations being evaluated visually.
The following examples are given to better illustrate the present invention and are not to be considered as limitative of its scope, which is defined by the accompanying claims.
100 g of the composition ET19 according to the invention were prepared, it consisting of:
a) 85.8 g of COSMACOL ETI
b) 4.5 g of HYDROPHILIC PYROGENIC SILICA (WACKER HDK V15)
c) 4.7 g of COSMACOL EOI
d) 5.0 g of 1,2-PROPYLENEGLYCOL
The composition was prepared by mixing components a and b together under cold conditions using a mechanical stirrer or turboagitator. While agitating the obtained homogeneous solution with a turbomixer at moderate speed, component c and finally component d were added.
The appearance of the obtained compositions was determined visually: F=fluid, GT=transparent gel, GO=opaque gel. The viscosity (expressed in Pascal/second) was determined as described on page 6.
Following the procedure described in Example 1, a series of lipogels were prepared having the composition and viscosity and transparency characteristics given in the following tables (1-1a-1b-1c-1d-2-2a-2b).
The results show that only by mixing the components in determined proportions is it possible to obtain transparent formulations of particular viscosity.
The formulations with the required properties are marked with an asterisk.
TABLE 1
__________________________________________________________________________
LIPOGELS WITH COSMACOL ETI
ET1
ET2
ET3
ET4
ET5
ET6
ET7
ET8
ET9
ET10
ET11
Component % by weight
__________________________________________________________________________
Cosmacol ETI
96 93.1
91.1
96.5
93.1
90.2
87.4
85.5
94.0
93.6
92.1
Hydrophobic silica
2 1.9
1.9
2.0
4.9
4.8
4.6
4.5
5.0
4.9 6.9
PEG 200 2 5 7 -- 2 5 8 10 1 -- 1
Glycerin -- -- -- 1.5
-- -- -- -- -- 1.5 --
APPEARANCE
F F F F GT*
GT*
GT*
GT*
GT*
G0 GT*
VISCOSITY
(50 rpm) 15.2
14.0
12.8
11.6
12,0
10.8
37.6
(20 rpm,) 3.2
3.0
3.0
2.0
__________________________________________________________________________
TABLE 1a
__________________________________________________________________________
LIPOGELS WITH COSMACOL ETI
ET12
ET13
ET14
ET15
ET16
ET17
ET18
ET38
ET39
ET40
Component % by weight
__________________________________________________________________________
Cosmacol ETI
91.1
90.2
85.6
95.5
91.7
93.1
90.2
92.1
92.1
92.1
Hydrophobic silica
6.9 6.8 6.4 3.5 3.3 4.9 4.8 -- -- --
Hydrophilic silica
-- -- -- -- -- -- -- 6.9 6.9 6.9
PEG 200 2 3 8 1 5 -- -- 1 -- --
Propyleneglycol
-- -- -- -- -- 2 5 -- 1 --
Glycerin -- -- -- 1.5 -- -- -- -- -- 1
APPEARANCE
GT* GT* GT* F F F F GT* GT* GT*
VISCOSITY
(50 rpm) 36.0
32.0
25.6
-- -- -- -- 68.0
36.8
64.0
(20 rpm) 5.0 5.8 5.0 7.5
__________________________________________________________________________
TABLE 1b
__________________________________________________________________________
LIPOGELS WITH COSMACOL ETI
ET20
ET21
ET22
ET23
ET24
ET25
ET26
ET27
ET28
Component % by weight
__________________________________________________________________________
Cosmacol ETI
90.4
90.8
89.5
90.9
90.6
95.0
94.1
93.6
89.0
Hydrophilic silica
4.8 4.5 5.5 38 3.9 4.0 3.9 3.9 3.9
PEG 200 4.8 4.8 5.0 -- -- -- -- -- --
Propyleneglycol
-- -- -- 5.4 -- -- -- -- 7.2
Glycerin -- -- -- -- 1.5 1.0 2.0 2.5 --
APPEARANCE
GT* GT* GT* GT* GT* GT* GT* GT* GT*
VISCOSITY 18.4
13.5
21.6
-- 25.0
20.0
18.0
26.5
--
(50 rpm)
__________________________________________________________________________
TABLE 1c
__________________________________________________________________________
LIPOGELS WITH COSMACOL ETI
ET19
ET29
ET30
ET31
ET32
ET33
ET34
ET35
ET36
Component % by weight
__________________________________________________________________________
Cosmacol ETI
85.8
88.5
88.5
88.5
88.5
95.5
94.9
93.8
89.2
Hydrophobic silica
-- 4.7 4.7 4.7 4.7 -- -- -- --
Hydrophilic silica
5.0 -- -- -- -- 3.0 2.9 2.9 2.8
PEG 200 4.5 2.0 2.0 2.0 2.0 -- 2.2 -- --
Propyleneglycol
-- -- -- -- -- -- -- 3.3 3.2
Glycerin -- -- -- -- -- 1.5 -- -- --
Cosmacol EOI
4.7 -- -- -- -- -- -- -- --
Cosmacol ECI
-- 4.9 -- -- -- -- -- -- --
White oil -- -- -- 4.9 -- -- -- -- --
Jojoba oil
-- -- 4.9 -- -- -- -- -- 4.8
Eusolex 4360
-- -- -- -- 4.9 -- -- -- --
APPEARANCE
GT* GT* GT* GT* GT* GT* GT* GT* GT*
VISCOSITY 22.5
13.2
16.0
13.6
13.0
10.4
8.0 6.5 5.6
(50 rpm)
__________________________________________________________________________
TABLE 1d
__________________________________________________________________________
LIPOGELS WITH COSMACOL ETI
ET37
ET41
ET42
ET43
ET45
ET46
ET47
ET48
Component % by weight
__________________________________________________________________________
Cosmacol ETI
89.2
87.5
91.1
83.7
46.0
46.0
46.0
46.0
Hydrophilic silica
2.8 6.6 6.9 6.3 3.5 3.2 3.2 3.2
PEG 200 -- 1.0 -- -- 1.0 -- 1.0 --
Propyleneglycol
3.2 -- 1.0 0.9 -- 1.0 -- 1.0
White oil 4.8 -- -- -- 49.5
49.5
-- --
Jojoba oil
-- -- -- -- -- -- 49.5
49.5
Almond oil
-- 4.0 -- -- -- -- -- --
Eusolex 4360
-- -- 1 -- -- -- -- --
Parsol MCX
-- -- -- 9.0 -- -- -- --
APPEARANCE
GT* GT* GT* GT* GT* GT* GT* GT*
VISCOSITY 5.2 63.0
60.0
20.0
8.0 7.2 7.6 6.4
(50 rpm)
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
TRANSPARENT GELS WITH COSMACOL EMI
EM1
EM2
EM3
EM4
EM5
EM6
EM7
EM8
EM9
EM10
EM11
Component % by weight
__________________________________________________________________________
Cosmacol EMI
92.9
90.2
87.4
93.6
93.1
89.8
91.7
96.0
93.1
90.2
94.1
Hydrophobic silica
4.9
4.8
4.6
4.9
4.9
4.7
4.8
2.0
1.9
1.8 4.9
PEG 200 2.2
5.0
8.0
-- -- -- -- 2.0
5.0
8.0 1.0
Glycerin -- -- -- 1.5
-- -- -- -- -- -- --
Ethylene glycol
-- -- -- -- 2.0
5.5
3.5
-- -- -- --
APPEARANCE
GT*
GT*
GT*
G0 GT*
G0*
G0*
F F F GT*
VISCOSITY
(50 rpm) 12.0
12.0
16.0
10.5
12.0
7.2
13.6
-- -- -- 8.0
(20 rpm,) -- -- -- -- -- -- -- 2.5
2.5
2.5 --
__________________________________________________________________________
TABLE 2a
______________________________________
TRANSPARENT GELS WITH COSMACOL EMI
EM12 EM13 EM18 EM19 EM20
Component % by weight
______________________________________
Cosmacol EMI
90.3 90.2 88.4 91.0 92.2
Hydrophilic silica
4.7 5.1 6.7 6.9 6.9
PEG 200 5.0 4.7 -- 2.2 --
Glycerin -- -- -- -- 0.9
Propylene glycol
-- -- 4.9 -- --
APPEARANCE GT* GT* F GT* G0
VISCOSITY
(50 rpm) 23.0 11.0 -- 4.8 7.6
(20 rpm,) -- -- 6.0 -- --
______________________________________
TABLE 2b
______________________________________
TRANSPARENT GELS WITH COSMACOL EMI
EM14 EM15 EM17
Component % by weight
______________________________________
Cosmacol EMI 88.5 88.5 88.5
Hydrophobic silica
4.7 4.7 4.7
PEG 200 2.0 2.0 2.0
Cosmacol ECI 4.9 -- --
Jojoba oil -- 4.9 --
White oil -- -- 4.9
APPEARANCE GT* GT* GT*
VISCOSITY
(50 rpm) 7.2 7.6 6.0
(20 rpm,) -- -- --
______________________________________
Claims (11)
1. A transparent lipogel formulation for cosmetic and pharmaceutical use, characterised by a viscosity of between 4.8 and 68 Pa.s and consisting essentially of:
A) an ester selected from the group consisting of:
--tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 46 and 95 wt %, and
--malic acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 87 and 95 wt %;
B) an oil or ester selected from the group consisting of:
--2-ethyl-hexanoic acid alkyl (C12 -C13 single-branch) ester,
--2-hydroxy-1,2,3-propanetricarboxylic acid alkyl (C12 -C13 single-branch) triester,
--white oil,
--jojoba oil,
--benzophenone-6
--ethylhexyl-p-methoxy-cinnamate, and
--sweet almond oil,
in a quantity of between 0 and 46 wt %;
C) hydrophilic or hydrophobic pyrogenic silica in a quantity of between 2.8 and 7.0 wt. %;
D) a polyalcohol selected from the group consisting of:
--polyethyleneglycol 200 (PEG),
--ethyleneglycol,
--1,2-propyleneglycol, and
--glycerin,
in a quantity of between 1 and 10 wt %, said components A), B), C) and D) being present in amounts that result in a transparent lipogel.
2. A formulation in accordance with claim 1, characterised by a viscosity of between 11 and 36 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 85 and 95 wt %;
C) hydrophobic pyrogenic silica in a quantity of between 4.5 and 7.0 wt %;
D) polyethyleneglycol 200 in a quantity of between 2 and 10 wt %.
3. A formulation in accordance with claim 1, characterised by a viscosity of between 13 and 68 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 89 and 95 wt %;
C) hydrophilic pyrogenic silica in a quantity of between 3.6 and 7.0 wt %;
D) polyethyleneglycol 200 in a quantity of between 1 and 5 wt %.
4. A formulation in accordance with claim 1, characterised by a viscosity of between 13 and 68 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 89 and 96 wt %;
C) hydrophilic pyrogenic silica in a quantity of between 3.9 and 4.0 wt %;
D) glycerin in a quantity of between 1 and 2.5 wt %.
5. A formulation in accordance with claim 1, characterised by a viscosity of between 13 and 68 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols 89.0 wt %
C) hydrophilic pyrogenic silica 3.9 wt %
D) 1,2-propyleneglycol 7.2 wt %.
6. A formulation in accordance with claim 1, characterised by a viscosity of 22.5 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols 85.8 wt %
B) 2-ethyl-hexanoic acid alkyl (C12 -C13 single-branch) ester 4.7 wt %
C) hydrophilic pyrogenic silica 5.0 wt %
D) polyethyleneglycol 200 4.5 wt %.
7. A formulation in accordance with claim 1, characterised by a viscosity of between 13.0 and 16 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols 88.5 wt %
B) an oil or ester selected from the group consisting of:
--2-hydroxy-1,2,3-propanetricarboxylic acid alkyl (C12 -C13 single-branch) triester,
--benzophenone-6,
--white oil, and
--jojoba oil, in a quantity of 4.9 wt %;
C) hydrophobic pyrogenic silica 4.7 wt %
D) polyethyleneglycol 200 2.0 wt %.
8. A formulation in accordance with claim 1, characterised by a viscosity of between 5.2 and 63 Pa.s and having the following composition:
A) tartaric acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 46 and 95.5 wt %;
B) an oil or ester selected from the group consisting of:
--white oil,
--jojoba oil,
--benzophenone-6, and
--ethylhexyl-p-methoxy-cinnamate, in a quantity of between 1 and 49.5 wt. %;
C) hydrophilic pyrogenic silica in a quantity of between 2.9 and 6.9 wt %;
D) a polyalcohol selected from the group consisting of:
--polyethyleneglycol 200,
--1,2-propyleneglycol, and
--glycerin, in a quantity of between 1 and 3.3 wt %.
9. A formulation in accordance with claim 1, characterised by viscosity of between 12 and 16 Pa.s and having the following composition:
A) malic acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 90.2 and 94.1 wt %;
C) hydrophobic pyrogenic silica in a quantity of between 4.6 and 4.9 wt %;
D) a polyalcohol selected from the group consisting of:
--polyethyleneglycol 200, and
--ethyleneglycol, in a quantity of between 2 and 8 wt %.
10. A formulation in accordance with claim 1, characterised by a viscosity of between 4.8 and 23.0 Pa.s and having the following composition:
A) malic acid diester of C12 -C13 single-branch fatty alcohols in a quantity of between 90.2 and 94.1 wt %;
C) hydrophilic pyrogenic silica in a quantity of between 4.7 and 6.9 wt %;
D) polyethyleneglycol 200, in a quantity of between 4.8 and 23 wt %.
11. A formulation in accordance with claim 1, characterised by a viscosity of between 6.0 and 7.6 Pa.s and having the following composition:
A) malic acid diester of C12 -C13 single-branch fatty alcohols in a quantity of 88.5 wt %;
B) an oil or ester selected from the group consisting of:
--2-hydroxy-1,2,3-propanetricarboxylic acid alkyl (C12 -C13 single-branch) triester,
--white oil, and
--jojoba oil, in a quantity of 4.9 wt %;
C) hydrophobic pyrogenic silica in a quantity of 4.7 wt %;
D) polyethyleneglycol 200, in a quantity of 2 wt %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI93A1610 | 1993-07-21 | ||
| ITMI931610A IT1270953B (en) | 1993-07-21 | 1993-07-21 | TRANSPARENT OIL-BASED GELS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5597576A true US5597576A (en) | 1997-01-28 |
Family
ID=11366648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/274,447 Expired - Fee Related US5597576A (en) | 1993-07-21 | 1994-07-13 | Oil-based transparent gels |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5597576A (en) |
| EP (1) | EP0635260A1 (en) |
| JP (1) | JPH07145037A (en) |
| CZ (1) | CZ174994A3 (en) |
| IT (1) | IT1270953B (en) |
| SK (1) | SK279411B6 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5736505A (en) * | 1996-08-30 | 1998-04-07 | Dragoco, Inc. | Non-alcoholic perfume or cologne |
| US20020103280A1 (en) * | 1999-10-26 | 2002-08-01 | Lassila Kevin Rodney | Malic acid diester surfactants |
| US20050050636A1 (en) * | 2003-09-04 | 2005-03-10 | Hiroto Setokawa | Pillow |
| US20050223493A1 (en) * | 2003-09-04 | 2005-10-13 | Sumitomo Rubber Industries, Ltd. | Pillow |
| US20060069167A1 (en) * | 2004-09-30 | 2006-03-30 | Jutaro Shudo | 1-chloro-2,4-dinitrobenzene gel compositions and methods for using the same |
| US20060111451A1 (en) * | 2004-09-30 | 2006-05-25 | Jutaro Shudo | 1-Chloro-2,4-dinitrobenzene gel compositions and methods for using the same |
| US20110021398A1 (en) * | 2008-05-30 | 2011-01-27 | Evonik Stockhausen Gmbh | Skin and hand cleansers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2734719B1 (en) * | 1995-05-30 | 1997-07-11 | Oreal | USE OF COLLOIDAL SILICIC ACID IN A COMPOSITION IN OILY MEDIA AND COMPOSITION OBTAINED |
| DE69600181T3 (en) * | 1995-05-30 | 2002-09-05 | L'oreal S.A., Paris | Use of colloidal silica to reinforce keratin fibers |
| JP3589514B2 (en) * | 1995-09-22 | 2004-11-17 | 株式会社ノエビア | Non-aqueous gel skin cleanser |
| JP3589513B2 (en) * | 1995-09-22 | 2004-11-17 | 株式会社ノエビア | Massage cosmetics |
| DE19615038A1 (en) * | 1996-04-17 | 1997-10-23 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations containing triazine derivatives and dialkyl esters of alpha, beta-dihydroxycarboxylic acids |
| US5759527A (en) * | 1996-10-02 | 1998-06-02 | Colgate-Palmolive Company | Hair conditioning composition |
| FR2768053B1 (en) * | 1997-09-09 | 1999-10-15 | Oreal | PHOTOPROTECTIVE COMPOSITIONS COMPRISING A BENZYLIDENE CAMPHOR AND / OR A DIBENZOYLMETHANE AND / OR A TRIAZINE AND A DIALKYL TARTRATE; COSMETIC USES |
| US5904917A (en) * | 1997-09-12 | 1999-05-18 | Colgate-Palmolive Company | Sun protection composition |
| DE19756076A1 (en) * | 1997-12-17 | 1999-06-24 | Henkel Kgaa | Skin care products for oily skin |
| DE19820109C2 (en) * | 1998-05-06 | 2000-05-18 | Wella Ag | Hair treatment agent with alpha-hydroxycarboxylic acid esters and polymers and their use |
| ITMI981579A1 (en) * | 1998-07-10 | 2000-01-10 | Condea Augusta Spa | DETERGENT COMPOSITION WITH SOFTENING AND PROTECTIVE ACTION OF NATURAL FIBERS |
| US7025957B2 (en) * | 2002-09-06 | 2006-04-11 | Desert Whale Jojoba Company | Composition and method to whiten skin |
| DE102004039726A1 (en) * | 2004-08-16 | 2006-03-02 | Beiersdorf Ag | Cosmetic preparation, useful e.g. for the protection of sunlight, as a make-up product in the decorative cosmetic and day- and night cream, comprises UV light protection filter and oil components with hydroxyl group |
| JP2012087107A (en) * | 2010-10-22 | 2012-05-10 | Natural Invention Kk | Silica-containing gel composition, anti-inflammatory agent, water-retaining agent and cosmetic |
| SG11201501711TA (en) * | 2012-09-07 | 2015-04-29 | Pibed Ltd | Surfactant and solvent-free heavy duty skin cleanser |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5082103A (en) * | 1974-01-22 | 1975-07-03 | ||
| US4078147A (en) * | 1975-09-10 | 1978-03-07 | The Nisshin Oil Mills, Ltd. | Hydroxy acid esters of higher alcohols |
| US4840788A (en) * | 1986-07-15 | 1989-06-20 | Ici Americas Inc. | Nonalcoholic sunscreen gel |
| EP0357186A2 (en) * | 1988-06-25 | 1990-03-07 | Beecham Group Plc | Skin and hair-care compositions |
| US5000945A (en) * | 1986-04-22 | 1991-03-19 | Ajinomoto Co., Inc. | Method of stabilizing a UVB absorbing compound, a stabilized UV absorber, and a cosmetic composition containing the same |
| US5073573A (en) * | 1987-09-25 | 1991-12-17 | Giulini Chemie Gmbh | Gel compositions and cosmetic/compositions containing the same |
| JPH0459716A (en) * | 1990-06-27 | 1992-02-26 | Noevir Co Ltd | Oily gelatinous cosmetic |
| US5141964A (en) * | 1989-08-23 | 1992-08-25 | Roussel Uclaf | Cosmetic compositions and method |
| US5258136A (en) * | 1992-03-04 | 1993-11-02 | Application Chemicals, Inc. | Alkoxylated compounds and their use in cosmetic stick formulations |
-
1993
- 1993-07-21 IT ITMI931610A patent/IT1270953B/en active IP Right Grant
-
1994
- 1994-07-13 US US08/274,447 patent/US5597576A/en not_active Expired - Fee Related
- 1994-07-14 EP EP94202053A patent/EP0635260A1/en not_active Withdrawn
- 1994-07-20 CZ CZ941749A patent/CZ174994A3/en unknown
- 1994-07-21 JP JP6190169A patent/JPH07145037A/en not_active Withdrawn
- 1994-07-21 SK SK886-94A patent/SK279411B6/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5082103A (en) * | 1974-01-22 | 1975-07-03 | ||
| US4078147A (en) * | 1975-09-10 | 1978-03-07 | The Nisshin Oil Mills, Ltd. | Hydroxy acid esters of higher alcohols |
| US5000945A (en) * | 1986-04-22 | 1991-03-19 | Ajinomoto Co., Inc. | Method of stabilizing a UVB absorbing compound, a stabilized UV absorber, and a cosmetic composition containing the same |
| US4840788A (en) * | 1986-07-15 | 1989-06-20 | Ici Americas Inc. | Nonalcoholic sunscreen gel |
| US5073573A (en) * | 1987-09-25 | 1991-12-17 | Giulini Chemie Gmbh | Gel compositions and cosmetic/compositions containing the same |
| EP0357186A2 (en) * | 1988-06-25 | 1990-03-07 | Beecham Group Plc | Skin and hair-care compositions |
| US5141964A (en) * | 1989-08-23 | 1992-08-25 | Roussel Uclaf | Cosmetic compositions and method |
| JPH0459716A (en) * | 1990-06-27 | 1992-02-26 | Noevir Co Ltd | Oily gelatinous cosmetic |
| US5258136A (en) * | 1992-03-04 | 1993-11-02 | Application Chemicals, Inc. | Alkoxylated compounds and their use in cosmetic stick formulations |
Non-Patent Citations (4)
| Title |
|---|
| Chemical Abstracts, vol. 117, No. 10, Sep. 7, 1992, Columbus, Ohio, US; abstract No. 97110f, T. Shoko "transparent oily cosmetic gels" & JP-A-4 059 716 (Noebia K.K.) Feb. 26, 1992. |
| Chemical Abstracts, vol. 117, No. 10, Sep. 7, 1992, Columbus, Ohio, US; abstract No. 97110f, T. Shoko transparent oily cosmetic gels & JP A 4 059 716 (Noebia K.K.) Feb. 26, 1992. * |
| Database WPI, Week 7647, Derwent Publications Ltd., London, GB; AN 76 87425X & JP A 50 082 103 (Nisshin Oils Mills KK) Jul. 3, 1975. * |
| Database WPI, Week 7647, Derwent Publications Ltd., London, GB; AN 76-87425X & JP-A-50 082 103 (Nisshin Oils Mills KK) Jul. 3, 1975. |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5736505A (en) * | 1996-08-30 | 1998-04-07 | Dragoco, Inc. | Non-alcoholic perfume or cologne |
| US20020103280A1 (en) * | 1999-10-26 | 2002-08-01 | Lassila Kevin Rodney | Malic acid diester surfactants |
| US6969738B2 (en) | 1999-10-26 | 2005-11-29 | Air Products And Chemicals, Inc. | Malic acid diester surfactants |
| US20050050636A1 (en) * | 2003-09-04 | 2005-03-10 | Hiroto Setokawa | Pillow |
| US20050223493A1 (en) * | 2003-09-04 | 2005-10-13 | Sumitomo Rubber Industries, Ltd. | Pillow |
| US20060069167A1 (en) * | 2004-09-30 | 2006-03-30 | Jutaro Shudo | 1-chloro-2,4-dinitrobenzene gel compositions and methods for using the same |
| US20060111451A1 (en) * | 2004-09-30 | 2006-05-25 | Jutaro Shudo | 1-Chloro-2,4-dinitrobenzene gel compositions and methods for using the same |
| CN101005813B (en) * | 2004-09-30 | 2010-11-03 | 帝国制药美国公司 | 1-chloro-2, 4-dinitrobenzene gel compositions and methods of use thereof |
| US8080261B2 (en) * | 2004-09-30 | 2011-12-20 | Teikoku Pharma Usa, Inc. | 1-chloro-2,4-dinitrobenzene non-aqueous gel compositions and methods for using the same |
| US20110021398A1 (en) * | 2008-05-30 | 2011-01-27 | Evonik Stockhausen Gmbh | Skin and hand cleansers |
| US8211841B2 (en) | 2008-05-30 | 2012-07-03 | Evonik Stockhausen Gmbh | Skin and hand cleansers |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI931610A1 (en) | 1995-01-21 |
| SK279411B6 (en) | 1998-11-04 |
| JPH07145037A (en) | 1995-06-06 |
| EP0635260A1 (en) | 1995-01-25 |
| IT1270953B (en) | 1997-05-26 |
| SK88694A3 (en) | 1995-03-08 |
| CZ174994A3 (en) | 1995-02-15 |
| ITMI931610A0 (en) | 1993-07-21 |
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